Lubricant additive and composition containing same



3,089,851 LUBRICANT ADDITIVE AND COMPOSITION CONTAINING SAME Donald L. Klass, Barrington, 111., and Roger W. Watson, Highland, and Robert E. Karl], Munster, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Filed Dec. 8, 1958, Ser. No. 778,606 18 Claims. (Cl. 252-321) This invention relates to additive compositions for use in lubricating oils, the use of such additive compositions, and improved lubricating compositions containing such additive compositions and intended for use in internal combustion engines such as diesel engines and automobile engines. More particularly the invention relates to additive compositions which impart detergency and antirust properties to lubricating oils and suppress preignition, excess varnish formation, and octane requirement increase when used in lubricating oils.

Straight petroleum lubricants are effective within certain defined limits of engine operating conditions and when these limits are exceeded, such lubricants frequently fail to give the desired performance demanded of them. Since, in modern engines designed to give increased performance, these limits are.frequently exceeded, the use of straight mineral oils as lubricants produce undesirable conditions within the engine; thus varnish formation, corrosion, preignition, and octane requirements are all excessive in modern engines using mineral oils alone.

It is an object of the present invention to provide a new composition for use as a lubricant additive. It is another object to provide a lubricating oil additive composition which imparts detergency, preignition and octane requirement increase suppression, anti-varnish formation and anti-rust properties to a lubricating oil. It is a further object of the present invention to provide a lubricating oil having these properties and suitable for usein a modern internal combustion engine. Other objects and advantages of our present invention will be ap parent from the descriptions and examples set out below.

We have discovered that a hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be reacted with an amine compound and a boron compound to form a new composition of matter with desirable characteristics for use as an additive composition in a lubricating oil. When used in a lubricating oil in even very small amounts, i.e. in amounts as low as .0001 wt. percent and preferably not exceeding 20 wt. percent, the boron and amine-containing additive composition of our present invention overcomes the problems of the mineral lubricating oil in its use without additives by imparting to the lubricating oil high detergency properties and eliminating excessive varnish formation and corrosion, while suppressing preignition and octane requirement increase. The new composition may also be used in an additive concentrate in amounts of from 10 to 50 weight percent or more for addition to lubricating oils.

Broadly, our present invention provides an additive composition for lubricating oils formed by reacting a hydrolyzed phosphorus sulfide-hydrocarbon reaction product with at least a sufficient amount of an amine compound to 'neutralize the reaction product and then reacting the resulting neutralized reaction product with a boron compound, i.e. boric acid. Our invention also provides an improved mineral oil containing an effective amount of our additive composition to impart improved properties to the lubricating oil.

The amine compound used in preparing the additive composition of our present invention may be any aliphatic or substituted aliphatic compound having 1 or more basic amine groups. Preferred amine compounds par- United States Patent 3,089,851 Patented May 14, 1963 'ice ticularly suited for use in the preparation of the additive composition of our present invention are the hydroxy aliphatic amines such as monohydroxy, dihydroxy, and polyhydroxy aliphatic amines and particularly preferable are the aliphatic polyamines such as diamines, triamines, etc., having two or more carbon atoms in the aliphatic chain. Polyhydroxy aliphatic polyamines are includable in either group. Particularly suitable aliphatic polyamines are alkylene polyamines containing at least two primary amino nitrogen atoms. Examples of alkylene polyamines suitable for the hereindescribed purpose are ethylene diamine, propylene diamine, diethylene triamine, diamylene triamine, triethylene tetramine, tripropylene tetramine, diethylene propylene tetramine, tetraethylene pentamine, tetrabutylene pentamine, diethylenedipropylene pentamine, butylene diamine, dihexylene triamine, and the like, or mixtures thereof. For example, a suitable polyamine product is a crude diethylene triamine containing minor amounts of ethylene diamine and triethylene tetramine. Other suitable aliphatic polyamines include those having the general formula RNH( CH NH in which R is preferably a C to C aliphatic chain, and which are obtained by condensing the suitable amine with acrylonitrile and hydrogenating to the corresponding diamine. Commercially available aliphatic polyamines of this type are those marketed by Armour and Company as Duomeens, which are prepared by the condensation of a dodecyl (Coco) amine or an octadecyl (tallow) amine with acrylonitrile followed by hydrogenation to the corresponding diamine product; these products are marketed as Duomeen C and Duomeen T, respective ly.

The hydrolyzed phosphorus sulfide-hydrocarbon reaction product may be prepared by any method known to the prior art. We prefer to react a hydrocarbon with from about 1% to about 50%, and preferably from about 5% to about 25% of phosphorus sulfide at a temperature of from about 200? F. to about 600 F. in a non-oxidizing atmosphere, as, for example, in a nitrogen atmosphere. The reaction is carried out for from about one to about ten hours or more, and preferably for about five hours. The reaction may be carried out in the presence of a sulfurizing agent such as sulfur, sulfur chlorides, etc., if desired. The product is hydrolyzed at a temperature of from about 200 F. to about 500 F., and preferably at a temperature of from about 300 F. to about 400 F. by hydrolyzing means, for example, by introducing steam through the reaction mixture. The hydrolyzed product may be solvent extracted to remove salts of inorganic phosphorus acids and low molecular weight organic phosphorus acids formed during hydrolysis. Solvent extraction may be accomplished in accordance with the method described by Norman E. Lemmon et al. in US. 2,843,579, issued July 15, 1958.

In the phosphorus sulfide-hydrocarbon reaction used for preparing starting materials for the additive compositions of the present invention, any phosphorus sulfides such as P 5 P 5 P 8 or other phosphorus sulfides and preferably phosphorus pentasulfide, P 8 may be reacted with a hydrocarbon.

The hydrocarbons used in the phosphorus sulfidehydrocarbon reaction may be polymers such as monoolefin polymers, copolymers, graft polymers, etc. and may also be unpolymerized or unpolymerizable hydrocarbons such as olefins, paraflins, cycloparaffins, aromatic hydrocarbons, etc.

The mono-olefin polymer to be treated may be the polymer resulting from the polymerization of low molec ular weight mono-olefins preferably the isomono-olefins, such as isobutylene and isoamylene and/or the copolymers obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins of less than six carbon atoms and preferably those of four carbon atoms. The polymer may be obtained by the polymerization of these olefins or mixed olefins in the presence of catalysts such as sulfuric acid, phosphoric acid, or boron fluoride, aluminum chloride or other similar halide catalysts of the Friedel-Crafts type.

The polymers are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing monoand isomonoolefins, such as butylene and isobutylene at a temperature of from about 80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel-Crafts type, such as for example, boron fluoride, aluminum chloride, and

the like. In the preparation of these polymers, a hydrocarbon mixture containing isobutylene and butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline can be used. The polymers may be treated directly with phosphorus sulfide to form a reaction product or alternatively the polymers may be fractionated under reduced pressure to obtain fractions of desired molecular weights.

Suitable polymers, for example, which may be used in the present invention arethe low molecular weight polymers having molecular weights of from about 150- to about 2000 or higher such as those low molecular weight polymers prepared by the liquid phase polymerization of a hydrocarbon mixture containing butanes and butylenes and being principally isobutylene and normal butylene, at a temperature of from about F. to about 100 F.', using an aluminum chloride catalyst.

Suitable hydrocarbon polymers may also be prepared by polymerizing a gaseous hydrocarbon mixture containing isobutylene and normal butylene in the presence of a phosphoric acid catalyst in the synthesis of isooctane at temperatures of from about 270 F. to about 430 F., and preferably from about 300 F. to about 330 F., and at a pressure in the range of about 500 p.s.i. to about 750 p.s.i. The product obtained is a mixed polymer comprising principally a dimer but also containing a minor proportion of heavier polymer such as trimer, tetramer and higher polymers. The polymer mixture may be separated into fractions as desired by distillation.

As a starting material there can be used the polymer or synthetic lubricating oil obtained by polymerizing the unsaturated hydrocarbons resulting from the vapor phase cracking of paraffin waxes in the presence of aluminum chloride which is fully described in US. Patents Nos. 1,955,260; 1,970,402; and 2,091,398. Still another type of olefin polymer which may be employed is the polymer resulting from the treatment of vapor phase cracked gasoline and/or gasoline fractions with, sulfuric acid or solid adsorbents, such as fullers earth, whereby the unsaturated polymerized hydrocarbons are removed. Also contemplated within the scope of this invention is the treatment with phosphorus sulfide of the polymers resulting from the voltolization of hydrocarbons as described for example in US. Patents Nos. 2,197,768 and 2,191,787.

Other hydrocarbons which we can use as reactants in the preparation of the phosphorus sulfide reaction product are parafiins, olefins, aromatics or alkyl aromatics, cyclic aliphatics, petroleum fractions, such as lubricating oil fractions, petrolatums, waxes, cracking cycle stocks, condensation products of the foregoing hydrocarbons, solvent extracts of petroleum extracts, etc.

The parafiin hydrocarbons can be those obtained from petroleum oils such as bright stock residuums, lubricating oil distillates, petrolatums, or paraffin waxes. We may also halogenate any of the foregoing paratlins and condense the same with aromatic hydrocarbons in the presence of anhydrous inorganic halides such as aluminum chloride, zinc chloride, boron fluoride and the like.

As examples of high molecular weight olefinic hydrocarbons which we may employ as reactants are cetene (C cerotene (C melene (C and mixed high nilolecular weight alkenes obtained by cracking petroleum o s.

Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms in a long chain. Such olefins can be obtained by the dehydrogenation of paraflins, such as by the cracking of paraflin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parafiin waxes.

More particularly, the additive composition concentrates of our present invention are formed by neutralizing hydrolyzed phosphorus sulfide hydrocarbon reaction product formed, for example as indicated above and preferably solvent extracted, with an amine compound having 2 or more carbon atoms and preferably selected from the group consisting of hydroxy aliphatic amines and aliphatic polyamines as defined above. The neutralized product is then reacted with a boron compound, preferably in amounts corresponding to from about 1 to about 3 moles boron per mole of neutralized product. The boron compound is boric acid and may be used in the forms of boric acid, boric acid anhydride and a boric acid ester which decomposes to give boric acid in situ. We add up to about 1.1 moles of amine compound per mole of acid phosphorus in the hydrolyzed reaction product depending on the type of amine compound used. It is preferred to neutralize only one amine group of a given amine compound and, therefore, from about 1 to about 1.1 moles of the amine compound per mole of acid phosphorus is preferred. The boron reaction is carried out in the presence of a suitable solvent for the boron compound such as dioxane, dimethylformamide, or other suitable solvent. During the boron reaction, it may be advantageous to stir the mixture of neutralized reaction product and boron compound and to warm the mixture for a short period of time, for example about one hour, to increase the solubility of the boron compound. The reaction mixture is then heated to a temperature above C. to strip otf water and allow the boron reaction to go to completion. We have found that when water is not stripped off the reaction is reversible and will not go to completion due to the instability of the boron reaction product in the presence of water. During warming, the reaction mixture should not be heated to a temperature at which the amine is driven from the mixture. If temperatures higher than the boiling point of the amine are used means for retaining the amine, such as, for example, refluxing, should be employed. An alternative method of forming the boron-containing amine-neutralized reaction products which we have found acceptable is by first reacting the boron compound with the amine compound and then reacting the resulting product with the phosphorus sulfide-hydrocarbon reaction product.

After the water has been driven off and the reaction is completed, the reaction mixture is treated for removal of solvent by placing the mixture in a vacuum or by passing nitrogen gas or other inert gases through the reaction mixture at a temperature sufficient to strip solvent therefrom. One to six hours is generally sufficient to strip the solvent out; however, this period of time is dependent on the amount and temperature of the stripping gas used as well as the nature of the solvent. In the case where a lower boiling solvent such as dioxane has been used it may be necessary to remove only traces of solvent by stripping with inert gas since much of the solvent will have been removed at the time water was driven from the mixture. The nitrogen blowing generally results in the formation of a clear product having dispersed impurities essentially removed. However, if the product should be hazy due to the presence of impurities, for example the presence of excess boron compound which has not reacted with the neutralized phosphorus sulfide hydrocarbon reaction product or has not dissolved therein, it may be desirable to filter the product through diatomaceous earth to obtain a suitably clear product The products formed in the above boron reaction contain chemically bonded boron.

The additive composition, prepared in accordance with the preferred method set out above, may be used in lubrieating oils in varying amounts constituting minor proportions of the total lubricating composition. The amount of additive used should be in excess of .0001 weight percent. We have found that the additive is effective in imparting improved detergency to lubricating oils even when used in such small amounts as range from about .01 weight percent to about 0.2 weight percent. However, it is preferred to add the additive composition to the lubricating oil in amounts of from about one weight percent to about weight percent although much greater amounts even above weight percent may be advantageously employed. The additive when used in a lubricating oil in an internal combustion engine was also found to suppress the octane requirement increase of the engine probably by entering the combustion chamber by the process of the blow-by.

As specific embodiments of our invention, the following examples are given by way of illustration and are not intended as limitations.to the invention.

HYDROLYZED INTERMEDIATE A hydrolyzed phosphorus sulfide-hydrocarbon reaction product is prepared by reacting about 15.5 wt. percent P 8 with a butylene polymer having a molecular weight of about 750-800 at a temperature of about 450 F. in a nitrogen atmosphere. The reaction is continued for about five hours for product formation. The product had a phosphorus content of about 4.3% and a sulfur content of about 7.5%. The reaction product formed is then hydrolyzed with steam at a temperature of about 300 F. to about 400 .F. The hydrolyzed product was diluted, for ease of handling, to about a 60% concentrate with a solvent extracted Mid-Continent 5W mineral oil having a viscosity of about 38 S.S.U. at 210 F. The resulting product ,was used as a starting material for the preparation of additives in subsequent examples.

Example 1 In accordance with the present invention the hydrolyzed intermediate was solvent extracted with isopropanol and water and reacted with one mole of ethylene diamine per mole of hydrolyzed reaction product. The resulting basic amine salt was treated with one mole of boric acid dissolved in dioxane. The mixture was stirred at 60 to 80 C. for 1 hour and then warmed to 100 to 110 C. Excess dioxane was distilled from the mixture and remaining traces of dioxane were removed by blowing with nitrogen. The product was an oil soluble clear composition containing 1.79% phosphorus.

Example 2 The hydrolyzed intermediate was solvent extracted with isopropanol and water and reacted with Duomeen T, an amine marketed by Armour Chemical Division and consisting of a propylene diamine having a side chain derived from tallow fatty acid and melting in the range of from 44 to 48 C. The resulting salt was treated with one mole of boric acid dissolved in dioxane. The mixture was stirred at 60 to 80 C. for one hour and then warmed to 100-1l0 C. to drive ofif water. Excess dioxane was distilled from the mixture and remaining traces of dioxane were removed by blowing with nitro gen gas. The product was clear and oil soluble and contained 1.57% phosphorus.

Example 3 The hydrolyzed intermediate was solvent extracted with isopropanol and water and treated with an equimolar amount of ethanol amine to produce a neutral salt. The neutral salt was then reacted with about 1 mole of boric acid dissolved in dimethylformamide. The mixture was stirred and heated at about 140 C. for a few hours and then stripped of solvent at 180 C. by blowing with nitrogen. The product was filtered through Celite to obtain a clear oil-soluble boron-containing detergent having a phosphorus content of 1.95%.

Example 4 Again in accordance with the present invention, the hydrolyzed intermediate was solvent extracted with isopropanol and water and treated with an equimolar amount of triethanol amine. The resulting neutral salt was treated with about 3 moles of boric acid dissolved in dimethyl formamide. The mixture was stirred and heated to about 140 C. for a few hours and then stripped of solvent at 180 C. by blowing with nitrogen. A clear oil-soluble product containing 1.80% phosphorus was obtained by filtration through Celite.

The compositions of the above examples were compared by tests particularly directed toward the determination of detergency. The tests as outlined below with results given demonstrate such characteristics of the additives of the present invention under conditions of use hibition, preignition prevention, octane requirement increase inhibition, rust prevention, corrosion inhibiton, etc.

The compositions of the present invention were comparatively subjected to a detergency screening test which rates detergency by a determination of piston varnish deposits. The test was carried out in a current model Chevrolet powerglide engine operating for one hour at 500 r.p.m. and no load and for 6 subsequent hours at 2500 r.p.m. and a load of 45 B.H.P. The oil temperature for the first hour was F., for the second and third hours was F. and for the 4 remaining hours was 220 F. The water temperature for the first 3 hours was from 85 to 95 F., and for the remaining 4 hours was to F. Each 7 hours so constituted is regarded a cycle. For the detergency screening tests, 4 cycles were run with a 4-hour rest between each cycle. At the end of the 4 cycles, the pistons were examined for varnish and rated on a scale whereby pistons free of varnish are rated 10 and pistons having very heavy varnish are rated one. The following samples were subjected to the above test and the comparative results are indicated in Table I.

Sample A.3.74 weight percent of the product of Example l in a phenol extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. Sample A contained .067 wt. percent phosphorus.

Sample B.4.27 weight percent of the product of Example 2 in a phenol extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. Sample B contained .067 wt. percent phosphorus.

Sample C.3.43 weight percent of the product of Example 3 and 0.75 weight percent of sulfurized dipentene in a phenol extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. Sample C contained .067 wt. percent phosphorus.

Sample D.3.73 weight percent of the product of Example 4 and 0.75 weight percent of sulfurized dipentene in a phenol extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. Sample D contained .067 wt. percent phosphorus.

Example E.3.9 weight percent of a barium containing neutralized phosphorus pentasulfide butylene polymer (mol. wt. of about 750 to 800) reaction product 1 and 0.79 weight percent of sulfurized dipentene in a solvent extracted Mid-Continent mineral oil containing a polyisobutylene polymer viscosity index improver and having a viscosity of about 62 S.S.U. at 210 F. Sample E had a total phosphorus con-tent of .055 wt. percent.

Example F.6.6 weight percent of a barium-containing neutralized phosphorus pentasulfide-butylene polymer (mol. wt. of about 750 to 800) reaction product 1 and 0.75 weigh-t percent of sulfurized dipentene in a solvent extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. Sample F had a total phosphorus content of 0.135 wt. percent.

Example G.A phenol extracted Mid-Continent base stock mineral oil having a viscosity of about 45 S.S.U. at 210 F. and containing no additives.

TABLE I Results of Detergency Screening Test Sample: Piston varnish rating A 8.5 B 8.8 C 8.7 D 9.1 E 7.2 F 7.4 G 5.9-6.3

As can be seen from Table I' the compositions of the present invention indicated as Samples -A, B, C, and D when used in commercial-type lubricating compositions as well as when used with a mineral-oil alone gave superior piston varnish rating results when compared with metal-containing detergent additives as exemplified by Samples E and F as compounded in commercial-type lubricants. The compositions of our invention also proved prover and having a viscosity of about 55 S.S.U. at

TABLE II Results of Preignition Test Preignition average counts Sample: per hour A 46 B 63 C 120-128 As can be seen with reference to Table II the compositions of our present invention showed less preignition under the above prescribed test conditions than did the prior art composition set out in Sample C of Table H.

An additive composition prepared in accordance with the present invention was added in an amount of 3.74% to a commercial lubricating oil and was tested for octane requirement increase in comparison with the lubricating oil alone. The test was conducted in a 1953 Oldsmobile engine at 1500 r.p.m. under full load (wide open throttle) for a period of time suflicient to attain octane requirement equilibrium (about 150 to 200 hrs.). During the test the oil temperature was about 175 F., the coolant temperature was about 165 F. and the air temperature at inlet and outlet was approximately 100 F. The test was run first using the additive-containing lubricating oil.- The octane requirement for the additive lubricating oil was recorded (before deposit removal). The octane of the fuel for the engine was increased until the audible preignition was substantially eliminated and the octane number required to substantially eliminate audible preignition was recorded. The engine was then dismantled and deposits were removed. The engine was reassembled and the octane requirement using the commercial lubrieating oil containing the additive of the present invention about 100 F. To test preignition, the engine was run using a primary reference fuel containing no lead until octane requirement equilibrium was reached, and then the engine was run under the same conditions using a leaded fuel. The average preignition counts per hour were recorded as indicated in Table II. For comparison a barium-containing detergent additive was also incorporated into a commercial-type lubricating oil and subjected to the preignition test. The following samples were tested and the results are given in Table II.

Sample A.3.74 wt. percent of the product of Example 1 in solvent extracted Mid-Continent SAE 5 mineral base oil contaiing a polymethacrylate-type viscosity index improver and having a viscosity of about S.S.U. at 210 F. 3

Sample B.4.27 wt. percent of the product of Example 2 in solvent extracted Mid-Continent SAE 5 mineral base oil containing a polymethacrylate-type viscosity index improver and having a viscosity of about 55 S.S.U. at 210 F. a

Sample C.3.3 wt. percent of a barium-containing neutralized phosphorus pentasulfide-butylene polymer (mol. wt. of about 750 to 800) reaction product in solvent extracted Mid-Continent SAE 5 mineral. base oil For comparison of metal-containing phosphorus sulfidehydrocarbon reaction products with the amine-containing boron complexes.

Having a phosphorus content of .067 wt. percent of the total components 0 the sample.

was again measured and recorded. The octane requirement increase was computed by subtracting the octane requirement after deposit removal from that before deposit removal. The additive of the present invention used for this test was the additive prepared in accordance with Example 1. The test was repeated for the commercial lubricating oil without an additive of the present invention. The results of the octane requirement increase test are shown in Table III below.

The composition of Example 5 prepared in accordance with the present invention was tested by a modified hydraulic valve lifter rust test and was compared with various other lubricating oil compositions as indicated in Table IV. The test was carried out in a current model Chevrolet powerglide engine operating at 2500 r.p.m. and

a load of 45 B.H.P. with an oil temperature of 120 F.

and a water temperature of from to F. The test was operated at these conditions for two hours with a 4 hour running and 4 hour ofl cycle. At the end of 20 hours the dip stick, rocker arms and valve lifters were inspected for rust. Valve lifters were rated on a graded basis from 1 to 10 whereby 10 indicates rust free valve lifters and 1 indicates badly rusted lifters. The samples listed below were tested and the results, shown below in Table IV, indicate superiority of the compositions of the present invention for rust inhibition.

Sample A.-3.73 wt. percent of the product of Example 4 and 0.75 wt. percent of sulfurized dipentene in a solvent extracted Mid-Continent SAE 5 mineral base oil containing a polymethacrylate viscosity index improver having a viscosity of about 55 S.S.U. at 210 F.

Sample B.A solvent extracted Mid-Continent base stock mineral oil having a viscosity of 45 S.S.U. at 210 F. and containing no additive.

Sample C.0.75 wt. percent of sulfurized dipentene in a solvent extracted Mid-Continent base stock mineral oil having a viscosity of 45 S.S.U. at 210 F.

Sample D.2.0 wt. percent of a barium-containing neutralized phosphorus pentasulfide butylene polymer (mol. Wt. of about 750 to 800) reaction product in a solvent extracted Mid-Continent base stock mineral oil having a viscosity of 45 S.S.U. at 210 F.

Sample B.Sarnple D containing 0.75 wt. percent of sulfurized dipentene.

' TABLE IV Results of Rust Test Sample Test, Dipstick Rocker Litters Hrs. Arms sulfurized dipentene in a solvent extracted mineral oil I basestock containing an isobutylene polymer viscosity index improver and having a viscosity of about 62 S.S.U. at 210 F. The varnish test was run on the compounded lubricant containing the product of Example 4 for a period of 231 hours before failure. In the same test, a commercial lubricant failed after only 154 hours of operation.

In the L4 engine test, designed for evaluating oxidation and corrosion characteristics of motor oils conducted according to the procedure specified by the CRC designation L-4-545, CRC Handbook 1946 edition, Coordinating Lubricants Research Council, New York, a composition of the present invention, i.e. the composition of Example 4 was compounded in a mineral oil base stock containing an isobutylene polymer viscosity index improver and having a viscosity of about 62 S.S.U. at 210 F. with a commercial zinc dialkyl dithiophosphate corrosion inhibitor having 8.3% zinc. The compounded lubricating oil contained the product of Example 5 in an amount of 3.73% and the zinc dialkyl dithiophosphate corrosion inhibitor in an amount of 1.25%. Briefly, the test procedure involved the operation of a special 6- cylinder automotive engine at constant speed and load for a period of 36 hours. The engine was operated at 3150 r.p.m.- 25 at an engine load of about 30 B.H.P. with a jacket coolant outlet temperature of 200 F. and an inlet temperature of 190 F. minimum. During the test the oil sump temperature is maintained at 265 to 280 F. At the end of the test period, the engine is dismantled and inspected for deposits of varnish and sludge and rated on a scale of 0 to 10, a rate of 10 denoting a clean engine free of deposits. The bearings are 10 weighed to determine bearing weight loss in grams during operation. The above composition was run under the conditions of this test and was given a varnish deposit rating of 8.5 and a sludge rating of 8.9. The bearing weight loss was 0.175 gram (an average of 2 runs).

The herein described additive compositions of the present invention can be used as indicated above in varying amounts of from .0001 up to about 20% in lubricating oils. Although the present invention has been illustrated by the use of the additive compositions in mineral lubricating oils, it is not restricted thereto. Other lubricating oil bases can be used, such as hydrocarbon oils, both natural and synthetic, for example, those obtained by the polymerization of olefins, as well as synthetic lubricating oils of the alkylene oxide type and the polycarboxylic acid ester type, such as the oil soluble esters of adipic acid, sebacic acid, azelaic acid, etc. It is also contemplated that various other well known additives, such as antioxidants, anti-foaming agents pourpoint depressors, extreme pressure agents, antiwear agents, may be incorporated in lubricating oils containing the additives of our invention.

Concentrates of a suitable oil base containing more than 10%, for example up to 50% or more, of the additives of this invention alone or in combination with other additives can be used for blending with hydrocarbon oils or other oils in the proportions desired for the particular conditions'of use to give a finished lubricating product containing the additives of this invention.

Unless otherwise stated, the percentages given herein a and in the claims are percentages by weight.

' tergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resulting phosphorus sulfidehydrocarbon reaction product; and reacting the hydrolyzed product with boric acid in an amount corresponding to from about one to about three moles boron per mole of hydrolyzed product and with an aliphatic amine compound having from 2 to 21 carbon atoms and selected from the group consisting of polyamines and hydroxy aliphatic amines in an amount corresponding to from about one to about 1.1 moles of aliphatic amine compound per mole of acid phosphorus, at a temperature below the temperature at which said aliphatic amine compound is driven from the mixture of reactants.

2. A lubricating composition comprising a major amount of hydrocarbon lubricating oil and from about 0.01 to about 20 weight percent of the composition of claim 1.

3. The composition of claim 1 wherein the boric acid is added to the reaction as boric acid per se.

4. The composition of claim 1 wherein the aliphatic amine compound is ethylene diamine.

5. The composition of claim 1 wherein the aliphatic amine compound is a propylene diamine having a side chain derived from tallow-fatty acid and melting in the range of 44 to 48 C.

6. The composition of claim 1 wherein the aliphatic amine compound is ethanolamine.

7. The composition of claim 1 wherein the aliphatic amine compound is triethanolamine.

8. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the proc- 1 1 ess comprising the steps of: reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; neutralizing the hydrolyzed product with an aliphatic amine compound having from 2 to 21 carbon atoms and selected from the group consisting of polyamines and hydroxy aliphatic amines in an amount corresponding to from about one to about 1.1 moles of aliphatic amine compound per mole of acid phosphorus; and reacting the neutralized product with boric acid in an amount corresponding to from about one to about three moles boron per mole of hydrolyzed product at a temperature below the temperature at which said aliphatic amine compound is driven from the mixture of reactants.

9. A lubricating composition comprising a major amount of a hydrocarbon lubricating oil and from about 0.01 to about 2.0 weight percent of the composition of claim 8.

10. The composition of claim 8 wherein the aliphatic amine compound is a hydroxy aliphatic amine.

11. The composition of claim 10 wherein the hydroxy aliphatic amine is triethanol amine.

12. The composition of claim 8 wherein the aliphatic amine compound is a polyamine.

13. The composition of claim 12 wherein the polyamine is ethylene diamine.

14. .As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps ofi reacting a phosphorus sulfide with a hydrocarbon; hydrolyzing the resultant phosphorus sulfide-hydrocarbon reaction product; reacting boric acid in an amount corresponding-to from about one to about three moles boron per mole of hydrolyzed product with an aliphatic amine compound having from 2 to 21 carbon atoms and selected from the group consisting of alkylene polyamines containing at least two primary amino nitrogen atoms and hydroxy aliphatic amines in an amount corresponding to from about one to about -1.1 moles of aliphatic amine compound per mole of acid phosphorus; and reacting the resulting boric acid aliphatic amine compound reaction product with the hydrolyzed phosphorus sulfide-hydrocarbon reaction product at a temperature below the temperature at which the aliphatic amine compound is driven from the mixture of reactants.

15. As a new composition of matter, an oil-soluble detergent neutralized reaction product prepared by the process comprising the steps of: reacting phosphorus sulfide with a butene polymer at a temperature of from about 200 F. to about 600 F.; hydrolyzing the resulting phosphorus sulfide-butene polymer reaction product; neutralizing the resulting hydrolyzed product with from about one to about 1.1 moles per mole of hydrolyzed reaction product of an aliphatic amine compound having from 2 to 21 carbon atoms and selected from the group consisting of alkylene polyamines containing at least two primary amino nitrogen atoms and having the formula RNH(CH NH wherein R is a C to C aliphatic chain and hydroxy aliphatic amines; reacting the resulting neutralized product with from about one to about three moles of boric acid per mole of neutralized product in the presence of a solvent for said boric acid at a temperature below the temperature at which the aliphatic amine compound is driven from the mixture of reactants; and heating the reactants to a temperature above C. to strip Water from the reaction mixture.

16. The composition of claim 15 wherein the solvent is a dioxane.

17. The composition of claim 15 wherein the solvent is dimethylformamide.

18. A lubricant additive concentrate consisting essentially of a hydrocarbon lubricating oil containing more than about 10% of an oil-soluble detergent neutralized reaction product prepared by the process comprising: reacting a phosphorus sulfide with a hydrocarbon; hydro lyzing the resulting phosphorus sulfide-hydrocarbon reaction product; and reacting the hydrolyzed product with boric acid in an-amount corresponding to from about one to about three moles boron per mole of hydrolyzed product and with an aliphatic amine compound having from 2 to 21 carbon atoms and selected from the group consisting of polyamines and hydroxy aliphatic amines in an amount corresponding to from about one to about 1.1 moles of aliphatic amine compound per mole of acid phosphorus at a temperature below the temperature at which the aliphatic amine compound is driven from the mixture of reactants. 

1. AS A NEW COMPOSITION OF MATTER, AN OIL-SOLUBLE DETERGENT NEUTRALIZED REACTION PRODUCT PREPARED BY THE PROCCESS COMPRISING: REACTING A PHOSPHORUS SULFIDE WITH A HYDROCARBON; HYDROLYZING THE RESULTING PHOSPHROUS SULFIDEHYDROCARBON REACTION PRODUCT; AND REACTING THE HYDROLYZED PRODUCT WITH BORIC ACID IN AN AMOUNT CORRESPONDING TO FROM ABOUT ONE TO ABOUT THREE MOLES BORON PER MOLE OF HYDROLYZED PRODUCT AND WITH AN ALIPHATIC AMINE COMPOUND HAVING FROM 2 TO 21 CARBON ATOMS AND SELECTED FROM THE GROUP CONSISTING OF POLYAMINES AND HYDROXY ALIPHATIC AMINES IN AN AMOUNT CORRESPONDING TO FROM ABOUT ONE TO ABOUT 1.1 MOLES OF ALIPHATIC AMINE COMPOUND PER MOLE OF ACID PHOSPHORUS, AT A TEMPERATURE BELOW THE TEMPERATURE AT WHICH SAID ALIPHATIC AMINE COMPOUND IS DRIVEN FROM THE MIXTURE OF REACTANTS. 